Process for producing brewers&#39; wort with enzymes



United States Patent M 3.353360 PROCESS FOR PRODUCKNG BREWERS WGRT WITHENZYMES Vincent 5. Bavisotto, Whitefish Bay, Wis, assignor to Chas.Pfizer & Co., Inc, New York, N.Y., a corporation of Delaware No Drawing.Fiied Nov. 1, 1966, Ser. No. 591,136 8 Claims. (Cl. 99-52) ABSTRACT OFTHE DESCLCSURE In the production of brewers wort, addition ofproteolytic enzyme to the malt (OJ-1.0% by weight based on weight ofmalt) permits the satisfactory use of maltzadjunct ratios as low as40:60. Diastatic enzyme and/or high diastatic malt is preferably addedto the mash when maltzadjunct ratio is 45:55 or less. Proteclytic restperiod can be reduced or eliminated by employing certain elevated mashtemperatures.

This application is a continuation-in-part of my earlier filed, pendingapplication Ser. No. 446,383, filed Apr. 7, 1965, which is in turn acontinuation-in-part of application Ser. No. 305,546, filed Aug. 29,1963, and now abandoned.

This invention relates to the production of brewers wort for use in themanufacture of non-distilled fermerited beverages such as beer, alelager, and the like. More particularly, it relates to the production ofbrewers wort and the fermented product obtained therefrom.

In the manufacture of beer and ale by the fermentation of cereals, suchas barley, the cereal is' subjected to a mashing process followed by afermentation process. In the manufacture of beer, for example, maltedbarley is traditionally used. Malted barley is made by the germinationof the barley, removal of the germ after drying, and crushing of theremaining grain. The malted barley is mixed with some other grain, suchas crushed corn or rice, and the mixture is treated with hot water at 7to 74 C. so that the amylase from the malted barley converts the starchof the grains into dextrins and fermentable sugars. The filtrate fromthis mixture is called the wort, and the residue is referred to as spentbrewers grain. The process as carried out to this point is oftenreferred to as mashing.

The wort is admixed with hops and boiled. The heat stops the action ofthe amylase and sterilizes the wort, while the extraction of the hopsprovides constituents which are flavor-producing and preservative. Thewort is thereafter cooled and subjected to fermentation by the additionof brewers yeast, Saccharomyces cerevisiae, or the like. A bottom yeastis usually used in beer manufacture and a top yeast for ale. A top yeastis one in which the cells gather in clumps and are carried to the top ofthe fermenting liquid by gas caught in the clumps, while the cells of abottom yeast stay fairly well separated and settle toward the bottom.The yeast utilizes the normally fermentable sugars which are part of thewort medium. The primary fermentation of the beer Wort occurs at about 7to 14 C. and ordinarily takes from seven to nine days. This is followedby the secondary or lager fermentation at 0 to 4 C. for two to six weeksor longer. Thereafter, the beer is clarified or filtered, carbonated andpackaged.

It is known that brewers wort is made from a mash of malt and adjunctssuch as prepared cereals, unmalted raw cereals, cereal grains such ascorn and rice or other carbohydrate source. Unmodified starches, such asraw corn grits, must be precooked in a separate cooker before beingadded to the mash. This is generally done by mixing them with Water andfinely ground malt. Said malt liquefies the starch material, thusenabling the complete conversion of starch to sugar in the main mash.

Heretofore, the generally acceptable mash in the brewing industry formaking beer, for example, was made up of about 65% malt and about 35%adjunct (corn) based on the total weight of malt and adjunct.

In some instances, mashes utilizing about 60% malt and about 40% adjunct(corn) have been used successfully. Based upon a maltzadjunct ratio of65:35 the brewing industry is able to set up a standardized brewingschedule, obtain consistent results in their product, and obtain a beerof desirable taste, body, stability, chemical composition, color, etc.The disadvantage of using a 65:35 (malt:adjunct) mash lies in the costinvolved, particularly with respect to the cost of malt.

It is known in the art that enzymes may be used in brewing. Nugey, forexample, US. 2,790,718, describes the addition of enzymes to a rawcereal-water mixture followed by heating said mixture to at least C. togelatinize and liquefy the cereal. The entire mass (cooker mash) is thencombined with a main malt mash to finish the beer. Dennis et al.,- inUS. 3,081,172, replaces malt as the primary enzymatic agent by theaddition of diastatic and proteolytic enzymes to a raw cereal mash, suchas unrnalted barley, which may contain up to 10% malt if desired. Inboth instances, however, raw or unmalted cereals are utilized.

The Nugey process completely inactivates the enzymes present at theelevated temperatures used with the result that when the cooker mash isadded to the main malt mash no active enzymes are present in the cookermash. The Dennis et a1. process is not used in the contemporaneousbrewing industry.

The novel process of the present invention, on the other hand, isspecifically designed for present-day brewing techniques and usesconventional brewing materials, i.e., malt and cereal adjunct. Thesalient feature of this process resides in the fact that it is the onlymethod which allows the present-day brewer to lower the malt to adjunctratios below the 65 :35 or 64:40 ratios now in use throughout thebrewing industry and still produce a beer of at least comparable qualityand at lower cost. Reduction of the malt level below that normally usedin the present-day brewing operations introduces nutrional deficienceswhich contributes to the development of diacetyl during fermentation.Indeed, this relationship becomes increasingly significant at low maltlevels resulting in beer of poor quality. Prior to the present inventionbeer made with malt to adjunct ratios other than 65:35 or 60:40 werecharacterized by sub-optimal nitrogen balance particularly as regardsthe formol nitrogen fraction. Such an 7 imbalance in turn affected yeastnutrition, brewing yield and increased diacetyl formation.

It has now been found that by adding specific enzymes to the mash, amash comprising 50:50 (maltzadjunct) ratio may be used in brewing. Sucha mash produces a beer of desirable taste, body, stability, chemicalcomposition, color, etc. comparable to and in some instances better thana beer produced from a 65:35 mash.

In a normal brewing operation any unmodified starches, such as corngrits, for example, are added to brewing water, placed in a cerealcooker and heated at about 70 C. for about 30 minutes. The mixture isthereafter brought to boiling and held there for about 10 minutes. Thecorn grits are completely liquefied by this treatment. To avoid highviscosity in the cooker, about 10% of the total malt may be added to thecorn grits. In accordance with the present invention the enzymeformulation is added to the mash tun which contains the malt and brewingwater. This mixture is held at about 37 C. for about one hour. At theend of this period, the proteolytic rest period, normal procedures arefollowed, i.e., the liquefied corn grits are added to the mash tun, thetemperature is raised to about 70 C., and the mixture held at thistemperature for an additional one-half to one hour. The gelatinizedstarch is converted into readily fermentable sugars and dextrine bycereal (diastatic) enzymes present in the malt.

It has further been found that the proteolytic rest time can be reducedsignificantly by the expedient of raising the mash temperature to up toabout 70 C. The standard proteolytic rest period is about 60' minutes atabout 37 C. The present novel process permits significant reduction and,by raising the mash temperature to about 60-70 C., even elimination ofthe proteolytic rest period. This novel and surprising improvement isapplicable to batch and continuous brewing processes. The worts producedhave approximately the same levels of total nitrogen and formol nitrogenas do worts produced by the standard procedures now in use in thebrewing industry.

At mash temperatures of about 35 to about 60 C. a proteolytic restperiod is used. That is, when operating within this temperature rangethe mash is raised to and held at a temperature of about 35 to about 60C. for a given period. The duration of the proteolytic rest perioddecreases as the temperature increases as is illustrated herein. At theupper temperature levels of this novel process, e.g. 60 to 70 C., theproteolytic rest period can be eliminated. The mash, after being raisedto this temperature level, is not held at said temperature but is passeddirectly to the next phase of the process in a continuous operation. Forthe purposes of this invention the use of a brief proteolytic restperiod, e.g. up to about 10 minutes, may be considered the equivalent ofa continuous process.

The come-up time, that is, the time required to raise the temperature ofthe mash to the desired levels of this novel process, depends, ofcourse, upon the equipment, the volume of material and the temperaturelevel used. The duration of the come-up time is not critical. As isobvious, the higher the temperature to which the mash is raised thelonger the come-up time. In general, when operating at a mashtemperature of about 60 to about 70 C. a come-up time of about 15minutes is required.

It is to be noted that, heretofore, all enzymatic activity was due tothe cereal (diastatic) enzymes and proteolytic enzymes present in themalt. This activity was satisfactory for producing a desirable beer aslong as the malt to adjunct ratio was about 65:35 and even as low as60:40. However, it was found that when the ratio dropped to about 55:45and even lower levels of malt, satisfactory beers were not obtained, andadditional enzymes had to be added to the mash. If additional enzyme wasnot added to the mash several undesirable results were manifested suchas unduly long conversion time, significantly lower extract yield, andlower nitrogen levels.

Following conversion of gelatinized starch to fermentable sugars anddextrins, the procedure is thereafter one which is generally practicedin the art, namely, the worts are transferred to a boiling kettle, hopsare added, and the worts are concentrated by boiling. The worts arethereafter aerated and pitched at 12 C. with brewing yeast. After theworts are pitched, they are placed intermentation vessels and allowed toferment at about 13 C. After fermentation the beers are removed tocolder C.) storage for yeast settling. Following yeast settling thebeers are decanted and placed in ruh storage for to 7 days at about 0 C.Thereafter, the beers are filtered, finished and bottled.

This invention applies to a normal brewing operation. Whereas heretoforethe ratio of malt to adjunct was substantially 65 :35 in the mash tun,or unmalted cereal grains plus an added enzyme comprised the mash, theinstant invention comprises replacing part of the malt with an addedenzyme. T he process is limited to the use of malted cereal andadjuncts.

It is to be understood that the ratio of malt to adjunct in the instantinvention need not be limited to 50:50. Ratios. as low as 40:60(maltzadjunct) and as high as 55:45 may be employed; however, it ispreferred that as the ratios drop to :55 and below, in addition to theproteolytic enzyme, the diastatic activity be supplemented, for example,by the addition of a diastatic enzyme, such as bacterial amylase, or bythe addition of high diastatic salt or both. An example of highdiastatic malt is distillers malt (a diastatic power (DP) of 190-250Lintner, alpha amylase (aa) of 70 units). The malt generally used in themanufacture of beer is brewers malt (a diastatic power (DP) of 120140Lintner, alpha amylase (aa) of 25-40 units).

Enzymes which have been found to be satisfactory include proteolyticenzymes such as papain, ficin, bromelain, pancreatin, and proteases,such as fungal and bacterial proteases. A satisfactory amount of enzymeto be used is from about 0.10% to about 1.0% by weight based on theweight of malt. An optimum amount of enzyme for a 50:50 brew is about0.16% by weight. The enzymes may be used.

The mash, containing malt and enzyme, is held at a temperature of fromabout 35 C. to about 70 C. for a period of up to about 90 minutes. Aspreviously noted, the duration of this period, the proteolytic restperiod, can be markedly reduced even to the point of elimination byraising the temperature of the mash. At temperatures of about to aboutC., for example, the proteolytic rest period can be reduced to about 10minutes or less as is exemplified herein. Following the addition of theliquefied corn to the mash, the temperature is then raised to from about65 C. to about C. and held at that temperature for a period of fromabout 30 minutes to about 60 minutes.

The invention may be more fully understod by reference to the followingexamples. It is to be understood that the examples are merely forillustration and are not limitations thereof.

Example I (50:50 ratio malt to com) Corn grits (1 88 g.) and brewersmalt (18.8 g.) are added to 700 ml. of brewing water and the whole isadded to a cooker. The cooker is brought to 70 C. and held at thistemperature for 30 minutes. The cooker is then brought to to C. and heldat this temperature for 10 minutes. The corn grits are liquefied by thistreatment.

To the mash tun are added 168.3 g. of brewers malt, 0.9 g. dark caramel.malt, 0.3 g. papain (1000 Hb units/ g.) and 700 ml. brewing water. Themash is brought to 37 C. and held there for 60 minutes (proteolytic restperiod). The liquefied corn is then added to the mash and thetemperature is increased to 70 C. and held there for 45 minutes. Themash is lautered and sparged with 1600 ml. of brewing water. Followinglautering and sparging the worts are transferred to the kettle. Threegrams of hops are added to the kettle and the worts are concentrated toa volume of 2000 ml. by boiling. The worts are cooled to 20 C. bycirculation through cooling coils, are aerated, and pitched at 12 C.with brewers yeast, Saccharomyces cerevisiae. The worts are stored inglass fermentation vessels and allowed to ferment at 13.5 C. After 5days the beers are removed and placed in cold storage (0 C.) for yeastsettling. After the yeast has settled, the beers are decanted off theyeast and placed in ruh storage for 5 to 7 days at 0 C. At the end ofruh storage, the beers are subjected to chemical analysis and tastetesting.

Example II The procedure of Example I is followed using ficin as theadded enzyme.

Example III The procedure of Example I is followed using brome lain asthe added enzyme.

Brewing water c0mp0sltionto 12 liters of water add 5 ml. 50% lactic acid(edible grade) and 6 g. Burton salts.

2 HelllOglOblH' (Hb) units per gran11nodified Alison's heinog'loblnmethod.

5 Example IV Ruh beers from Examples I, H and III are analyzed forchemical composition and the results are compared to a beer made from a65:35 maltzadjunct mash.

Ex. I Ex. II Ex. 65:35 III Brew Color,Lovibcnd 2. 27 2. 25 2.30 2. 16Apparent Extract, percent 2.86 2. 86 2. 88 2. 66 Real Extract, percent4. 69 4. 61 4. 64 4. 55 Alcohol by weight, percent... 3. 79 g 3. 66 3.66 3. 84 Alcohol by volume, percent. 4. 85 4. 68 4. 68 4. 91 OriginalExtract, percent 12.0 11.7 11. 7 12. Real Degree of Fermentation,percent 61. 1 60. 7 60. 4 62. 3 Apparent Degree of Fermentation,

percent 76. 0 75. 6 75. 5 77. 6 Acidity, percent 0.13 0.12 0.12 0.13 pH.4. 4 4. 4 4. 5 4. 5 Reducing Sugars, percent as maltose. 0.99 1. 04 0.99 0.90 DextrinS, percent 3.05 2. 88 2.98 2. 91 Total Protein percent (Nx 6.25) 0. 33 0. 38 0. 35 0. 35

Example V Example VIII The chemical composition results of ruh beersmade from a malt to corn ratio of 40:60 are compared with those madefrom a malt to corn ratio of 50:50 and 65 Malt to Corn Ratio Color,Lovibond 2. 40 2. 27 2. 16 Apparent Extract, percent 2. 97 2. 86 2. 66Real Extract, percent 4. 76 4. 69 4. Alcohol, weight, percent 3. 72 3.793. 84 Alcohol, volume, percent 4. 76 4. 85 4. 91 Original Extract,percent 12.0 12.0 12.0 Real Degree of Fermentation, percent 60. 3 61.162. 3 Apparent Degree of Fermentation, percent. 73. 0 76.0 77. 6Acidity, percent 0. 13 0. 13 0. 13 pH 4. 2 4. 4 4. 5 Reducing Sugars,percent as maltose 0. 97 O. 99 0. 90 Dextrins, percent 3.16 3. 05 2. 91Total protein, percent (N x 6.25).. 0.30 0.33 0. 35 Papain, percent(1000 Hb units/g.) 0.48 0. 16 0.00 Bacterial amylase, percent 2 O. 0130. O0 0. 00

Percent Enzyme Added to Mash Ex. I, 0.24 0.32

Color, Lovibond 2. 27 2. 08 2. 22 Apparent. Extract, pe en 2. 86 2. 433. 26 Real Extract, percent.. 4. 69 4.30 5. 05 Alcohol by weight, perce3. 79 3.98 3.80 Alcohol by volume, percent 4. 85 5. 08 4.87 Or ginalExtract, per cent.. 12.0 12.1 12.4 Real Degree of Fermentation, per 61.164.3 59.8 Apparent Degree of Fermentation, percen 76.0 76.8 72. 5Acidity, percent 0.13 0.13 0.14 pH. 4.4 4.5 4.5 Reducing Sugars, percentas maltose 0.99 0.88 1.04 Dextriris, percent 3.05 2. 76 3. 25 TotalProteins, percent (N x 6.25) 0.33 0.34 0.41

Example VI 1 Based on weight of malt. Added to mesh. Based on weight ofcorn. Added to mash.

Taste tests were conducted on beers after one week in ruh. The 50:50beers gave a slightly higher preference score than did the 65:35 beers.In general, all beers were found to be clean and neutral in aroma. Allhad light to moderate body and mild to moderate hop character and werevery acceptable forruh beers. The significantly lower level of malt inthe 50:50 beers resulted in a slightly lighter color than traditionalbeers. This may be compensated for by substituting different types ofcaramel malts such as black roasted malt (0.05%), dark caramel malt(0.5%), medium caramel malt (3%), light caramel malt (5%) and malt syrup(1.6%) for part of the regu lar malt. The percentages of the variouscaramel malts cited above are based on the weight of total malt. Flavorwas not affected by the addition of the caramel malts.

Type of Enzyme Used in the Mash Papain Ficin Bromelain Pancreatin FungalBacterial 65:35 Protease Protease Brew Conversion Time, min. arm" 0 4o41 40 41 40 39 Belling, Plato 12.1 11. 9 11. 9 10. 4 11.7 12.2 11.9Total Protein, Percent (N x 6.25) 0.53 0.54 0. 52 *N O 0.51 0.41 0.54Enzyme Cone. percent based on weight of malt. 0. 0. 16 0. 16 0.34 0. 160. 16 None Enzyme activ b units/gram l, 000 1, 000 1, 000 2, 048 1,00019 None 'NCnot calculated.

Example VII (40:60 ratio malt to corn) Corn grits (250 g.) and brewersmalt (16.7 g.) are added to 900 ml. brewing water, and the whole isadded to the cooker. The cooker is brought to 70 C. and held at thattemperature for 30 minutes. The cooker is then brought to 95 l00 C. andheld at this temperature for 10 minutes. The corn grits are liquefied bythis treatment. To the mash tun are added 121.3 g. brewers malt, 29 g.high diastic malt (240 Lintner), 25 g. soya flakes, 0.56 g. papain (1000Hb units/g), 0.066 g. bacterial amylase (35,000 D.V. units/g.) 4 g. maltsyrup and 500 ml. brewing water. The mash is brought up to 37 C. and

At malt levels of 45% and below, malt syrup may be added to augmentflavor as well as color.

In finished beers made thus far in breweries, it was found that beerflavor, chill haze and foam properties, were found to be comparable forthe 50:50 beer and the control. The colloidal stability of the 50:50beers was found to be superior to the controls both at low temperaturesand at room temperatures.

Example IX The procedure of Example I is repeated but using 0.16% ficin(1100 Hb units/g.) as the added enzyme based on the Weight of the maltand the following modifications in proteolytic rest period conditions.Pertinent data comparing the worts from these batches with that from abatch run under standard proteolytic rest conditions (60 minutes at 375C.) are recorded.

Proteolytlc Best Original Gm. N/lOO Gm. Foimol Extracts, m1., Wort N/100ml.,

percent Wort Temp. C.) Time (min) These data clearly demonstrate thatthe proteolytic rest period can be significantly reduced by raising themash temperature. In each instance approximately the same levels oftotal nitrogen and formol nitrogen are present in the worts.

Example X This example illustrates the production of worts by theprocedure of Example I using diiferent levels of ficin (1100 Hbunits/g.) as the added enzyme, a mash temperature of 70 C. and noproteolytic rest period. Pertinent data are recorded below.

Gm. N /100 Gm. Percent Proteolytic Rest Original ml., Formol FicinExtracts Wort N/100 ml.,

Wort

0.25."--- r 11. 0 0.0913 0. 039 0.50 11. 0 0. 1025 0. 0425 ControL. 37.50., 60 minutes. 11.0 0. 0840 0. 041

The nitrogen values in this example are higher due to the use of am'alt'blend brewed to a higher extract level.

Similar results are obtained at a mash temperature of 65 C. and noproteolytic rest arid at proteolytic' r'est conditions'of 5 C. for about20 minutes, 60 C. for about minutes.

Example The procedure of Example I is followed, two batches being run.In one batch, A, no proteol-ytic enzyme is added while in the secondbatch, B, 0.16% papain by weight is added. The beers thus produced givethe following results upon analysis.

Color, Lovibond 3. 85 3. 50 Apparent Extract, percent 2. 61 2. 62 RealExtract, percent 4. 24 4. 46 Alcohol, weight, percent 3. 46 3.60 Alcoholvolume, percen 4. 42 4.60 Original Extract, percen 11. 0' 11. 5 RealDegree of Fermentation, percent 61. 5 61. 2 Apparent Degree ofFermentation, percent 76. 3 77. 2 Acidity, percent 0.13 0. 12 pH 4. 254. 4 Reducing Sugars, percent, as maltose 1.00 0. 87 Dextrins, percent2.64 2. 89 Total protein, percent (N x 6. 25) 0.27 0.38 Diacetyl(p.p.rn.) 0. 41 0.27

The beer produced without the addition of proteolytic enzyme thus showstwo distinct abnormalities, loW protein content and high diacetylcontent whereas that produced with papain compares favorably with beersmade with a malt to corn ratio of :35.

What is claimed is:

1. In a process for making beer the improvement in preparing the wortwhich comprises the steps of adding proteolytic' enzyme to a malt mash,in amounts of from about 0.1% to about 1.0% by weight based on theweight of the malt,- raising the enzyme-containing mash to a temperatureof about 35 C. to about C., maintaining said temperature for a period offrom about 10 minutes up to about 90 minutes, thereafter addingliquefied cereal grain to said enzyme-containing mash in a proportion offrom about 45% to about 60% by weight based on the total weight of maltand cereal grain, raising the temperature of the entire mass to about 65C. to C. and maintaining the latter temperature for a period of fromabout 30 minutes to about 60 minutes.

2. A process as defined in claim 1 wherein the said enzyme is selectedfrom the group consisting of papain, ficin, bromelain, pancreatin,fungal protease, bacterial protease and mixtures thereof.

3. A process as in claim 1 wherein diastatic enzyme is included withsaid proteolytic enzyme whenever said cereal grain level is at least55%.

4. A process as defined in claim 1 wherein from about 0.16% to about0.25% by weight of a proteolyticenzyme based on the weight of malt isadded to a malt mash, and wherein the proportion of liquefied cerealgrain to said enzyme-containing mash is about 50%.

5. A process as defined in claim 4 wherein said proteolytic enzyme ispapain.

6. A process as defined inclaim 4' wherein said proteolytic enzyme isficin.

7. A process as defined in claim 4 wherein said proteolytic enzyme isbromelain.

8. In a process for making beer the improvement in the continuousproduction of wort which comprises the steps of adding proteolyt'ic enzyrne to a malt mash, raising the enzyme containing. mash to a temperatureof about 60 C. to about'70 C., thereafter adding liquefied cereal grainto said enzyme-containing. mash: in a proportion of from about 45% toabout about 60% by weight based on the total weight of malt and cerealgrain, raising the temperature of the entire mass to about 65 C. to 75C. and maintaining the latter temperature for a period of from. about30' minutes to about 60 minutes.

References Cited UNITED STATES PATENTS OTHER REFERENCES Nugey, A. L.,Brewers Manual Jersey Printing Co., Inc., New Jersey, TP N8, 1948 (page9).

A. LOUIS MONACELL, Primary Examiner.

D. M. NAFF, Assistant Examiner.

1. IN A PROCESS FOR MAKING BEER THE IMPROVEMENT IN PREPARING THE WORTWHICH COMPRISES THE STEPS OF ADDING PROTEOLYTIC ENZYME TO A MALT MASH,IN AMOUNTS OF FROM ABOUT 0.1% TO ABOUT 1.0% BY WEIGHT BASED ON THEWEIGHT OF THE MALT, RAISING THE ENZYME-CONTAINING MASH TO A TEMPERATUREOF ABOUT 35*C. TO ABOUT 70*C., MAINTAINING SAID TEMPERATURE FOR A PERIODOF FROM ABOUT 10 MINUTES UP TO ABOUT 90 MINUTES, THEREAFTER ADDINGLIQUEFIED CEREAL GRAIN TO SAID ENZYME-CONTAINING MASH IN A PROPORTION OFFROM ABOUT 45% TO ABOUT 60% BY WEIGHT BASED ON THE TOTAL WEIGHT OF MALTAND CERAL GRAIN, RAISING THE TEMPERATURE OF THE ENTIRE MASS TO ABOUT65*C. TO 75*C. AND MAINTAINING THE LATTER TEMPERATURE FOR A PERIOD OFFROM ABOUT 30 MINUTES TO ABOUT 60 MINUTES.